Colorants containing copolymerizable vinyl groups and sulfonamide linkages

Abstract

Disclosed are thermally-stable, colored, photopolymerizable compounds containing a vinyl group which are capable of being copolymerized with reactive vinyl monomers to produce colored compositions such as polyacrylates, polymethacrylates, polystyrene, etc. The compounds exhibit good thermal stability, fastness (stability) to UV-light, good solubility in the reactive monomers and good color strength.

We claim:  
     
       1. A photopolymerizable colorant compound having tie formula:                    
       wherein 
       A is a mono-, di-, tri- or tetravalent chromophore;  
       R 1  is hydrogen, C 1 -C 6  alkyl, substituted C 1 -C 6  alkyl, C 3 -C 8  cycloalkyl, aryl or —R 2 —OQ;  
       R 2  is C 2 -C 8  alkylene, arylene, C 3 -C 8  cycloalkylene, arylene-C 1 -C 6  alkylene, arylene-oxy-C 1 -C 6  alkylene, arylenethio-C 1 -C 6  alkylene, 1,4-cyclohexylenedimethylene or —(—CH 2 CH 2 O) m —CH 2 CH 2 —;  
       m is 1-3;  
       n is 1-4;  
       Q is an ethylenically-unsaturated, photopolymerizable group selected from the following organic radicals:                    
       wherein 
       R 3  is hydrogen or C 1 -C 6  alkyl;  
       R 4  is hydrogen, C 1 -C 6  alkyl; phenyl; phenyl substituted with one or more groups selected from C 1 -C 6  alkyl, C 1 -C 6  alkoxy, —N(C 1 -C 6  alkyl) 2 , nitro, cyano, C 2 -C 6  alkoxycarbonyl, C 2 -C 6  alkanoyloxy or halogen; 1- or 2-naphthyl; 1- or 2-naphthyl substituted with C 1 -C 6  alkyl or C 1 -C 6  alkoxy; 2- or 3-thienyl; 2- or 3-thienyl substituted with C 1 -C 6  alkyl or halogen; 2- or 3-furyl; or 2- or 3-furyl substituted with C 1 -C 6  alkyl;  
       R 5  and R 6  are independently selected from hydrogen, C 1 -C 6  alkyl, substituted C 1 -C 6  alkyl, aryl or may be combined to represent a —(—CH 2 —)— 3-5  radical;  
       R 7  is hydrogen or C 1 -C 6  alkyl, substituted C 1 -C 6  alkyl, C 3 -C 8  alkenyl, C 3 -C 8  cycloalkyl or aryl;  
       R 8  is selected from hydrogen, C 1 -C 6  alkyl or aryl; and  
       A is a chromophore selected from residues of anthraquinone, anthrapyridone, anthrapyrimidine, anthrapyridine, anthrapyrazole, anthraisothiazole, 14H-naptho[2,3-a]-phenothiazine-8,13-dione, methine, bis-methine, perinone, coumarin, quinophthalone, 3-aryl-2,5-dioxypyrroline, or 3-aryl-5-dicyanomethylene-2-oxypyrroline.  
     
     
       2. A photopolymerizable colorant according to  claim 1  having the formula                    
       wherein 
       R 1  is hydrogen, C 1 -C 6  alkyl, substituted C 1 -C 6  alkyl, C 3 -C 8  cycloalkyl, aryl or —R 2 —OQ;  
       R 2  is C 2 -C 8  alkylene, arylene, C 3 -C 8  cycloalkylene, arylene-C 1 -C 6  alkylene, arylene-oxy-C 1 -C 6  alkylene, arylenethio-C 1 -C 6  alkylene, 1,4-cyclohexylenedimethylene or —(—CH 2 CH 2 O) m —CH 2 CH 2 —;  
       m is 1-3;  
       n is 1-4;  
       R 15  is hydrogen or R 15  represents 1-4 groups selected from amino; C 1 -C 8 -alkylamino; C 1 -C 8 -alkylamino substituted with one or more of hydroxy, cyano, halogen, aryl, heteroaryl, C 3 -C 8 -cycloalkyl, furyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, arylthio, aryloxy or —OCH 2 CH 2 O(OCH 2 CH 2 ) 1-3 OR′, wherein R′ is hydrogen, C 1 -C 6 -alkyl or C 2 -C 6 -alkanoyloxy; C 3 -C 8 -cycloalkylamino; C 3 -C 8 -alkenylamino; C 3 -C 8 -alkynylamino; arylamino; furfurylamino; C 1 -C 6 -alkoxy; —OCH 2 CH 2 (OCH 2 CH 2 ) 1-3 OR′, wherein R′ is as previously defined; halogen; hydroxy; C 1 -C 6 -alkylthio; arylthio; aryl; aryloxy; arylsulfonyl; C 2 -C 6 -alkanoyl; aroyl; C 2 -C 6 -alkanoyloxy; C 2 -C 6 -alkoxycarbonyl; heteroaryl; heteroarylthio; cyano; nitro; trifluoromethyl; thiocyano; —SO 2 C 1 -C 6 -alkyl; —SO 2 NH 2 ; —SO 2 NHC 1 -C 6 -alkyl; —SO 2 N(C 1 -C 6  alkyl) 2 ; —SO 2 N(C 1 -C 6  alkyl)aryl; —SO 2 NH-aryl; —CONH 2 ; —CONHC 1 -C 6 -alkyl; —CON(C 1 -C 6 -alkyl) 2 ; —CONH-aryl; —CON(C 1 -C 6 alkyl) aryl; C 1 -C 6  alkyl; tetrahydrofurfurylamino; —CH 2 -cyclohexane-1,4-diyl-CH 2 OR′, wherein R′ is as previously defined; or                    
       R 16  is hydrogen or 1-2 groups selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy or halogen;  
       X is a covalent bond or a linking group selected from —O—, —S—, —SO 2 —, —NHCO—, —NHSO 2 —, —NHCONH—, —OC 2 -C 6  alkylene-, —OC 2 -C 6 -alkylene-O—, —S—C 2 -C 6 -alkylene-O— or, —O(CH 2 CH 2 O) 1-3 —; and  
       Q is an ethylenically-unsaturated, photopolymerizable group selected from the following organic radicals:                    
       wherein 
       R 3  is hydrogen or C 1 -C 6  alkyl;  
       R 4  is hydrogen, C 1 -C 6  alkyl; phenyl; phenyl substituted with one or more groups selected from C 1 -C 6  alkyl, C 1 -C 6  alkoxy, —N(C 1 -C 6  alkyl) 2 , nitro, cyano, C 2 -C 6  alkoxycarbonyl, C 2 -C 6  alkanoyloxy or halogen; 1- or 2-naphthyl; 1- or 2-naphthyl substituted with C 1 -C 6  alkyl or C 1 -C 6  alkoxy; 2- or 3-thienyl; 2- or 3-thienyl substituted with C 1 -C 6  alkyl or halogen; 2- or 3-furyl; or 2- or 3-furyl substituted with C 1 -C 6  alkyl;  
       R 5  and R 6  are independently selected from hydrogen, C 1 -C 6  alkyl, substituted C 1 -C 6  alkyl, aryl or may be combined to represent a —(—CH 2 —)— 3-5  radical;  
       R 7  is hydrogen, C 1 -C 6  alkyl, substituted C 1 -C 6  alkyl, C 3 -C 8  alkenyl, C 3 -C 8  cycloalkyl or aryl; and  
       R 8  is selected from hydrogen, C 1 -C 6  alkyl or aryl.  
     
     
       3. A photopolymerizable colorant according to  claim 1  having the formula                    
       wherein 
       R 1  is hydrogen or C 1 -C 6  alkyl;  
       R 2  is C 2 -C 8  alkylene, arylene, C 3 -C 8  cycloalkylene, arylene-C 1 -C 6  alkylene, arylene-oxy-C 1 -C 6  alkylene, arylenethio-C 1 -C 6  alkylene, 1,4-cyclohexylenedimethylene or —(—CH 2 CH 2 O) m —CH 2 CH 2 —;  
       m is 1-3;  
       R 16  is selected from 2′,6′-di-C 1 -C 6  alkyl; and  
       Q is —COC(R 3 )═CH 2  wherein R 3  is hydrogen or methyl.  
     
     
       4. A photopolymerizable colorant according to  claim 4  having the formula:                    
     
     
       5. A photopolymerizable colorant according to  claim 1  having the formula                    
       wherein 
       R 1  is hydrogen or C 1 -C 6  alkyl;  
       R 2  is C 2 -C 8  alkylene, arylene, C 3 -C 8  cycloalkylene, arylene-C 1 -C 6  alkylene, arylene-oxy-C 1 -C 6  alkylene, arylenethio-C 1 -C 6  alkylene, 1,4-cyclohexylenedimethylene or —(—CH 2 CH 2 O) m —CH 2 CH 2 —;  
       m is 1-3;  
       R 16  is selected from 2′,6′-di-C 1 -C 6  alkyl; and  
       Q is —COC(R 3 )═CH 2  wherein R 3  is hydrogen or methyl.  
     
     
       6. A photopolymerizable colorant according to  claim 1  having the formula                    
       wherein 
       R 1  is hydrogen, C 1 -C 6  alkyl, substituted C 1 -C 6  alkyl, C 3 -C 8  cycloalkyl, aryl or —R 2 —OQ;  
       R 2  is C 2 -C 8  alkylene, arylene, C 3 -C 8  cycloalkylene, arylene-C 1 -C 6  alkylene, arylene-oxy-C 1 -C 6  alkylene, arylenethio-C 1 -C 6  alkylene, 1,4-cyclohexylenedimethylene or —(—CH 2 CH 2 O) m —CH 2 CH 2 —;  
       m is 1-3;  
       R 17  is amino, C 1 -C 8 -alkylamino, substituted C 1 -C 8 -alkylamino as defined above, C 3 -C 8 -cycloalkylamino, C 3 -C 8 -alkenylamino, C 3 -C 8 -alkynylamino or arylamino;  
       R 18  is halogen, amino, C 1 -C 8  alkylamino, substituted C 1 -C 8 -alkylamino, C 3 -C 8 -cycloalkylamino, C 3 -C 8 -alkenylamino, C 3 -C 8 -alkynylamino, arylamino, hydroxy, arylthio, heteroarylthio, C 2 -C 6 -alkanoylamino, aroylamino, C 1 -C 6 -alkylsulfonylamino, or arylsulfonylamino; and  
       Q is an ethylenically-unsaturated, photopolymerizable group selected from the following organic radicals:                    
       wherein 
       R 3  is hydrogen or C 1 -C 6  alkyl;  
       R 4  is hydrogen, C 1 -C 6  alkyl; phenyl; phenyl substituted with one or more groups selected from C 1 -C 6  alkyl, C 1 -C 6  alkoxy, —N(C 1 -C 6  alkyl) 2 , nitro, cyano, C 2 -C 6  alkoxycarbonyl, C 2 -C 6  alkanoyloxy or halogen; 1- or 2-naphthyl; 1- or 2-naphthyl substituted with C 1 -C 6  alkyl or C 1 -C 6  alkoxy; 2- or 3-thienyl; 2- or 3-thienyl substituted with C 1 -C 6  alkyl or halogen; 2- or 3-furyl; 2- or 3-furyl substituted with C 1 -C 6  alkyl;  
       R 5  and R 6  are independently selected from hydrogen, C 1 -C 6  alkyl, substituted C 1 -C 6  alkyl, aryl or may be combined to represent a —(—CH 2 —)— 3-5  radical;  
       R 7  is hydrogen or a group selected from C 1 -C 6  alkyl, substituted C 1 -C 6  alkyl, C 3 -C 8  alkenyl, C 3 -C 8  cycloalkyl or aryl; and  
       R 8  is hydrogen, C 1 -C 6  alkyl or aryl.  
     
     
       7. A photopolymerizable colorant according to  claim 7  wherein 
       R 1  is hydrogen, C 1 -C 6  alkyl, or —R 2 —OQ;  
       R 2  is C 2 -C 8  alkylene, arylene, C 3 -C 8  cycloalkylene, arylene-C 1 -C 6  alkylene, arylene-oxy-C 1 -C 6  alkylene, arylenethio-C 1 -C 6  alkylene, 1,4-cyclohexylenedimethylene or —(—CH 2 CH 2 O) m —CH 2 CH 2 —;  
       m is 1-3;  
       R 17  is amino; C 1 -C 8 -alkylamino, substituted C 1 -C 8 -alkylamino as defined above, C 3 -C 8 -cycloalkylamino, C 3 -C 8 -alkenylamino, C 3 -C 8 -alkynylamino or arylamino;  
       R 18  is halogen, amino, C 1 -C 8  alkylamino, substituted C 1 -C 8 -alkylamino, C 3 -C 8 -cycloalkylamino, C 3 -C 8 -alkenylamino, C 3 -C 8 -alkynylamino, arylamino, hydroxy, arylthio, heteroarylthio, C 2 -C 6 -alkanoylamino, aroylamino, C 1 -C 6 -alkylsulfonylamino, or arylsulfonylamino; and  
       Q is —COC(R 3 )═CH 2  wherein R 3  is hydrogen or methyl.  
     
     
       8. A photopolymerizable colorant according to  claim 1  having the formula                    
       wherein 
       R 1  is hydrogen, C 1 -C 6  alkyl, or —R 2 —OQ;  
       R 2  is C 2 -C 8  alkylene, arylene, C 3 -C 8  cycloalkylene, arylene-C 1 -C 6  alkylene, arylene-oxy-C 1 -C 6  alkylene, arylenethio-C 1 -C 6  alkylene, 1,4-cyclohexylenedimethylene or —(—CH 2 CH 2 O) m —CH 2 CH 2 —;  
       m is 1-3;  
       R 15  is hydrogen, amino; C 1 -C 8 -alkylamino; C 1 -C 8 -alkylamino substituted with one or more groups selected from hydroxy, cyano, halogen, aryl, heteroaryl, C 3 -C 8 -cycloalkyl, furyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, arylthio, aryloxy or-OCH 2 CH 2 O (OCH 2 CH 2 ) 1-3 OR′, wherein R′ is selected from hydrogen, C 1 -C 6 -alkyl or C 2 -C 6 -alkanoyloxy; C 3 -C 8 -cycloalkylamino; C 3 -C 8 -alkenylamino; C 3 -C 8 -alkynylamino; arylamino; furfurylamino; C 1 -C 6 -alkoxy; —OCH 2 CH 2 —(OCH 2 CH 2 ) 1-3 OR′, wherein R′ is as previously defined; halogen; hydroxy; C 1 -C 6 -alkylthio; arylthio; heteroarylthio; thiocyano; tetrahydrofurfurylamino; —CH 2 -cyclohexane-1,4-diyl-CH 2 OR′, wherein R′ is as previously defined; or                    
       R 16  is hydrogen or 1-2 groups selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy or halogen;  
       X is —O—, —S—, —SO 2 —, or —O—C 2 -C 6  alkylene; and  
       Q is —COC(R 3 )═CH 2  wherein R 3  is hydrogen or methyl.  
     
     
       9. A photopolymerizable colorant according to  claim 1  having the formula                    
       wherein 
       R 1  is hydrogen, C 1 -C 6  alkyl, or —R 2 —OQ;  
       R 2  is C 2 -C 8  alkylene, arylene, C 3 -C 8  cycloalkylene, arylene-C 1 -C 6  alkylene, arylene-oxy-C 1 -C 6  alkylene, arylenethio-C 1 -C 6  alkylene, 1,4-cyclohexylenedimethylene or —(—CH 2 CH 2 O) m —CH 2 CH 2 —;  
       m is 1-3;  
       R 15  is hydrogen, C 1 -C 6 -alkoxy; —OCH 2 CH 2 (O CH 2 CH 2 ) 1-3 OR′, wherein R′ is hydrogen, C 1 -C 6 -alkyl or C 2 -C 6 -alkanoyloxy; halogen; hydroxy; C 1 -C 6 -alkylthio; arylthio; aryl; aryloxy; arylsulfonyl; C 2 -C 6 -alkanoyl; aroyl; C 2 -C 6 -alkanoyloxy; C 2 -C 6 -alkoxycarbonyl; heteroaryl; heteroarylthio; cyano; nitro; trifluoromethyl; thiocyano; —SO 2 C 1 -C 6 -alkyl; —SO 2 NH 2 ; —SO 2 NHC 1 -C 6 -alkyl; —SO 2 N(C 1 -C 6  alkyl) 2 ; —SO 2 N(C 1 -C 6  alkyl)aryl; —SO 2 NH-aryl; —CONH 2 ; —CONHC 1 -C 6 -alkyl; —CON(C 1 -C 6 -alkyl) 2 ; —CONH-aryl; and —CON(C 1 -C 6 alkyl) aryl;  
       R 16  is hydrogen or 1-2 groups selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy or halogen;  
       X is —NH— or —S—; and  
       Q is —COC(R 3 )═CH 2  wherein R 3  is hydrogen or methyl.  
     
     
       10. A photopolymerizable colorant according to  claim 1  having the formula                    
       wherein 
       R 1  is hydrogen, C 1 -C 6  alkyl, substituted C 1 -C 6  alkyl, C 3 -C 8  cycloalkyl, aryl or —R 2 —OQ;  
       R 2  is C 2 -C 8  alkylene, arylene, C 3 -C 8  cycloalkylene, arylene-C 1 -C 6  alkylene, arylene-oxy-C 1 -C 6  alkylene, arylenethio-C 1 -C 6  alkylene, 1,4-cyclohexylenedimethylene or —(—CH 2 CH 2 O) m —CH 2 CH 2 —;  
       m is 1-3;  
       n is 1-4;  
       R 15  is hydrogen or R 15  represents 1-4 groups selected from amino; C 1 -C 8 -alkylamino; C 1 -C 8 -alkylamino substituted with one or more groups selected from hydroxy, cyano, halogen, aryl, heteroaryl, C 3 -C 8 -cycloalkyl, furyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, arylthio, aryloxy or —OCH 2 CH 2 O (OCH 2 CH 2 ) 1-3 OR′, wherein R′ is selected from hydrogen, C 1 -C 6 -alkyl or C 2 -C 6 -alkanoyloxy; C 3 -C 8 -cycloalkylamino; C 3 -C 8 -alkenylamino; C 3 -C 8 -alkynylamino; arylamino; furfurylamino; C 1 -C 6 -alkoxy; —OCH 2 CH 2 (OCH 2 CH 2 ) 1-3 OR′, wherein R′ is as previously defined; halogen; hydroxy; C 1 -C 6 -alkylthio; arylthio; aryl; aryloxy; arylsulfonyl; C 2 -C 6 -alkanoyl; aroyl; C 2 -C 6 -alkanoyloxy; C 2 -C 6 -alkoxycarbonyl; heteroaryl; heteroarylthio; cyano; nitro; trifluoromethyl; thiocyano; —SO 2 C 1 -C 6 -alkyl; —SO 2 NH 2 ; —SO 2 NHC 1 -C 6 -alkyl; —SO 2 N(C 1 -C 6  alkyl) 2 ; —SO 2 N(C 1 -C 6  alkyl)aryl; —SO 2 NH-aryl; —CONH 2 ; —CONHC 1 -C 6 -alkyl; —CON(C 1 -C 6 -alkyl) 2 ; —CONH-aryl; —CON(C 1 -C 6 alkyl) aryl; C 1 -C 6  alkyl; tetrahydrofurfurylamino; —CH 2 -cyclohexane-1,4-diyl-CH 2 OR′, wherein R′ is as previously defined; or                    
       R 16  is hydrogen or 1-2 groups selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy or halogen;  
       R 19  is hydrogen, cyano, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, aryl, arylamino, aryloxy, arylthio, heteroaryl, heteroarylthio, halogen, C 2 -C 6 -alkoxycarbonyl, aroyl, C 1 -C 6 -alkylsulfonyl, arylsulfonyl or C 1 -C 6 -alkylamino;  
       R 20  is hydrogen, C 1 -C 8 -alkyl, substituted C 1 -C 8 -alkyl as defined above, aryl or C 3 -C 8 -cyloalkyl;  
       X is —NH—, —O—, —S—, —SO 2 —, or —O—C 2 -C 6  alkylene; and  
       Q is an ethylenically-unsaturated, photopolymerizable group selected from the following organic radicals:                    
       wherein 
       R 3  is hydrogen or C 1 -C 6  alkyl;  
       R 4  is hydrogen, C 1 -C 6  alkyl; phenyl; phenyl substituted with one or more groups selected from C 1 -C 6  alkyl, C 1 -C 6  alkoxy, —N(C 1 -C 6  alkyl) 2 , nitro, cyano, C 2 -C 6  alkoxycarbonyl, C 2 -C 6  alkanoyloxy or halogen; 1- or 2-naphthyl; 1- or 2-naphthyl substituted with C 1 -C 6  alkyl or C 1 -C 6  alkoxy; 2- or 3-thienyl; 2- or 3-thienyl substituted with C 1 -C 6  alkyl or halogen; 2- or 3-furyl; 2- or 3-furyl substituted with C 1 -C 6  alkyl;  
       R 5  and R 6  are independently selected from hydrogen, C 1 -C 6  alkyl, substituted C 1 -C 6  alkyl, aryl or may be combined to represent a —(—CH 2 —)— 3-5  radical;  
       R 7  is hydrogen or C 1 -C 6  alkyl, substituted C 1 -C 6  alkyl, C 3 -C 8  alkenyl, C 3 -C 8  cycloalkyl or aryl; and  
       R 8  is hydrogen, C 1 -C 6  alkyl or aryl.  
     
     
       11. A photopolymerizable colorant according to  claim 1  having the formula                    
       wherein 
       R 1  is hydrogen, C 1 -C 6  alkyl, or —R 2 —OQ;  
       R 2  is C 2 -C 8  alkylene, arylene, C 3 -C 8  cycloalkylene, arylene-C 1 -C 6  alkylene, arylene-oxy-C 1 -C 6  alkylene, arylenethio-C 1 -C 6  alkylene, 1,4-cyclohexylenedimethylene or —(—CH 2 CH 2 O) m —CH 2 CH 2 —;  
       m is 1-3;  
       R 15  is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, or halogen;  
       R 16  is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy or halogen;  
       R 19  is hydrogen, cyano, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, aryl, arylamino, aryloxy, arylthio, heteroaryl, heteroarylthio, halogen, C 2 -C 6 -alkoxycarbonyl, aroyl, C 1 -C 6 -alkylsulfonyl, arylsulfonyl or C 1 -C 6 -alkylamino;  
       R 20  is C 1 -C 8 -alkyl or substituted C 1 -C 8 -alkyl as defined above;  
       X is —NH— or —S—; and  
       Q is —COC(R 3 )═CH 2  wherein R 3  is hydrogen or methyl.  
     
     
       12. A photopolymerizable colorant according to  claim 1  having the formula                    
       wherein 
       R 1  is hydrogen, C 1 -C 6  alkyl, substituted C 1 -C 6  alkyl, C 3 -C 8  cycloalkyl, aryl or —R 2 —OQ;  
       R 2  is C 2 -C 8  alkylene, arylene, C 3 -C 8  cycloalkylene, arylene-C 1 -C 6  alkylene, arylene-oxy-C 1 -C 6  alkylene, arylenethio-C 1 -C 6  alkylene, 1,4-cyclohexylenedimethylene or —(—CH 2 CH 2 O) m —CH 2 CH 2 —;  
       m is 1-3;  
       n is 1-4;  
       R 15  is hydrogen or R 15  represents 1-4 groups selected from amino; C 1 -C 8 -alkylamino; C 1 -C 8 -alkylamino substituted with one or more groups selected from hydroxy, cyano, halogen, aryl, heteroaryl, C 3 -C 8 -cycloalkyl, furyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, arylthio, aryloxy or —OCH 2 CH 2 O(OCH 2 CH 2 ) 1-3 OR′, wherein R′ is selected from hydrogen, C 1 -C 6 -alkyl or C 2 -C 6 -alkanoyloxy; C 3 -C 8 -cycloalkylamino; C 3 -C 8 -alkenylamino; C 3 -C 8 -alkynylamino; arylamino; furfurylamino; C 1 -C 6 -alkoxy; —OCH 2 CH 2 (O CH 2 CH 2 ) 1-3 OR′, wherein R′ is as previously defined; halogen; hydroxy; C 1 -C 6 -alkylthio; arylthio; aryl; aryloxy; arylsulfonyl; C 2 -C 6 -alkanoyl; aroyl; C 2 -C 6 -alkanoyloxy; C 2 -C 6 -alkoxycarbonyl; heteroaryl; heteroarylthio; cyano; nitro; trifluoromethyl; thiocyano; —SO 2 C 1 -C 6 -alkyl; —SO 2 NH 2 ; —SO 2 NHC 1 -C 6 -alkyl; —SO 2 N(C 1 -C 6  alkyl) 2 ; —SO 2 N(C 1 -C 6  alkyl)aryl; —SO 2 NH-aryl; —CONH 2 ; —CONHC 1 -C 6 -alkyl; —CON(C 1 -C 6 -alkyl) 2 ; —CONH-aryl; —CON(C 1 -C 6 alkyl) aryl; C 1 -C 6  alkyl; tetrahydrofurfurylamino; or —CH 2 -cyclohexane-1,4-diyl-CH 2 OR′, wherein R′ is as previously defined;  
       R 16  is hydrogen or 1-2 groups selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy or halogen;  
       R 19  is hydrogen, cyano, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, aryl, arylamino, aryloxy, arylthio, heteroaryl, heteroarylthio, halogen, C 2 -C 6 -alkoxycarbonyl, aroyl, C 1 -C 6 -alkylsulfonyl, arylsulfonyl or C 1 -C 6 -alkylamino;  
       R 21  is hydrogen, C 1 -C 6 -alkyl, aryl or —N(R 22 )R 23 , wherein R 22  and R 23  independently are selected from hydrogen, C 3 -C 8 -cycloalkyl, C 1 -C 6 -alkyl or C 1 -C 6 -alkyl substituted with C 1 -C 6 -alkoxy, hydroxy, halogen, C 2 -C 6 -alkanoyloxy, aryl and C 3 -C 8 -cycloalkyl; or R 22  and R 23  in combination represent a divalent radical having the formulas (—CH 2 —) 4-6  or —CH 2 CH 2 —L—CH 2 CH 2 —, wherein L is a divalent linking group selected from —O—, —S—, —SO 2 — or —N(R 24 ), wherein R 24  is selected from hydrogen, C 1 -C 6 -alkyl, aryl, aroyl, C 2 -C 6 -akanoyl, C 1 -C 6 -alkylsulfonyl or arylsulfonyl;  
       X is —NH—, —O—, —S—, —SO 2 —, or —O—C 2 -C 6  alkylene; and  
       Q is an ethylenically-unsaturated, photopolymerizable group selected from the following organic radicals:                    
       wherein 
       R 3  is hydrogen or C 1 -C 6  alkyl;  
       R 4  is hydrogen, C 1 -C 6  alkyl; phenyl; phenyl substituted with one or more groups selected from C 1 -C 6  alkyl, C 1 -C 6  alkoxy, —N(C 1 -C 6  alkyl) 2 , nitro, cyano, C 2 -C 6  alkoxycarbonyl, C 2 -C 6  alkanoyloxy or halogen; 1- or 2-naphthyl; 1- or 2-naphthyl substituted with C 1 -C 6  alkyl or C 1 -C 6  alkoxy; 2- or 3-thienyl; 2- or 3-thienyl substituted with C 1 -C 6  alkyl or halogen; or 2- or 3-furyl; 2- or 3-furyl substituted with C 1 -C 6  alkyl;  
       R 5  and R 6  are independently selected from hydrogen, C 1 -C 6  alkyl, substituted C 1 -C 6  alkyl, aryl or may be combined to represent a —(—CH 2 —)— 3-5  radical;  
       R 7  is hydrogen, C 1 -C 6  alkyl, substituted C 1 -C 6  alkyl, C 3 -C 8  alkenyl, C 3 -C 8  cycloalkyl or aryl; and  
       R 8  is hydrogen, C 1 -C 6  alkyl or aryl.  
     
     
       13. A photopolymerizable colorant according to  claim 1  having the formula                    
       wherein 
       R 1  is hydrogen, C 1 -C 6  alkyl, or —R 2 —OQ;  
       R 2  is C 2 -C 8  alkylene, arylene, C 3 -C 8  cycloalkylene, arylene-C 1 -C 6  alkylene, arylene-oxy-C 1 -C 6  alkylene, arylenethio-C 1 -C 6  alkylene, 1,4-cyclohexylenedimethylene or —(—CH 2 CH 2 O) m —CH 2 CH 2 —;  
       m is 1-3;  
       R 15  is hydrogen, C 1 -C 6 -alkyl or halogen;  
       R 16  is hydrogen or 1-2 groups selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy or halogen;  
       R 19  is hydrogen or cyano;  
       R 21  is —N(R 22 )R 23 , wherein R 22  and R 23  are independently selected from C 1 -C 6 -alkyl or R 22  and R 23  in combination are a divalent radical having the formulas (—CH 2 —) 4-6  or —CH 2 CH 2 —L—CH 2 CH 2 —, wherein L is a divalent linking group selected from —O—, —S—, —SO 2 — or —N(R 24 ), wherein R 24  is selected from hydrogen, C 1 -C 6 -alkyl, aryl, aroyl, C 2 -C 6 -akanoyl, C 1 -C 6 -alkylsulfonyl or arylsulfonyl;  
       X is —NH— or —S—; and  
       Q is —COC(R 3 )═CH 2  wherein R 3  is hydrogen or methyl.  
     
     
       14. A coating composition comprising (i) one or more polymerizable vinyl compounds, (ii) one or more of the colorant compounds of  claim 1 , and (iii) a photoinitiator. 
     
     
       15. A coating composition according to  claim 15  comprising (i) one or more polymerizable vinyl compounds, (ii) one or more of the colorant compounds of  claim 2  present in a concentration of about 0.05 to 15 weight percent based on the weight of component (i), and (iii) a photoinitiator present in a concentration of about 1 to 15 weight percent based on the weight of the polymerizable vinyl compound(s) present in the coating composition. 
     
     
       16. A coating composition according to  claim 16  wherein the polymerizable vinyl compounds comprise a solution of a polymeric, polymerizable vinyl compound selected from acrylated or methacrylated polyesters, acrylated or methacrylated polyethers, acrylated or methacrylated epoxy polymers, acrylated or methacrylated urethanes, or mixtures thereof, in a diluent selected from monomeric acrylate or methacrylate esters. 
     
     
       17. A polymeric coating composition comprising a polymer of one or more acrylic acid esters, one or more methacrylic acid esters and/or other copolymerizable vinyl compounds, having copolymerized therein one or more of the colorant compounds defined in  claim 1 . 
     
     
       18. A polymeric coating composition according to  claim 17  comprising an acrylic polymer of one or more acrylic acid esters, one or more methacrylic acid esters or a mixture thereof having copolymerized therein one or more of the colorant compounds defined in  claim 2 . 
     
     
       19. A polymeric coating composition according to  claim 17  containing from about 0.05 to 15.0 weight percent of the residue of one or more of the dye compounds of  claim 2  based on the weight of the coating composition. 
     
     
       20. A polymeric coating composition according to  claim 17  wherein the polymer comprises an unsaturated polyester containing one or more maleate/fumarate residues; one or more monomers which contain one or more vinyl ether groups, one or more vinyl ester groups, or combination thereof, and, optionally, one or more acrylic or methacrylic acid esters; or a mixture thereof. 
     
     
       21. A photopolymerizable colorant having the formula:                    
       wherein 
       A is a residue of phthalocyanine or metal pthalocyanine;  
       R 1  is hydrogen, C 1 C 6  alkyl, substituted C 1 -C 6  alkyl, C 3 - C 8  cycloalkyl, aryl or —R 2 -OQ;  
       R 2  is C 2 -C 8  alkylene, arylene, C 3 -C 8  cycloalkylene, arylene —C 1 -C 6  alkylene, arylene—oxy—C 1 -C 6  alkylene, arylenethio —C 1 -C 6  alkylene, 1,4-cyclohexylenedimethylene or —(—CH 2 CH 2 O) m —CH 2 CH 2 —;  
       m is 1-3;  
       n is 1-4;  
       Q is —COC(R 3 )=CH-R 4 ;  
       R 2  is C 1 -C 6  alkyl; and  
       R 4  is hydrogen, C 1 -C 6  alkyl; phenyl substituted with one or more groups selected from C 1 -C 6  alkyl, C 1 -C 6  alkoxy, —N(C 1 -C 6  alkyl) 2 , nitro, cyano, C 2 -C 6  alkoxycarbonyl, C 2 -C 6  alkanoyloxy or halogen; 1- or 2-naphthyl; 1- or 2-naphthyl substituted with C 1 -C 6  alkyl or C 1 -C 6  alkoxy; 2- or 3-thienyl substituted with C 1 -C 6  alkyl or halogen; 2- or 3- furyl; or 2- or 3-furyl substituted with C 1 -C 6  alkyl.  
     
     
       22. A coating composition (i) one or more polymerizable vinyl compounds, (ii) one or more of the colorant compounds of  claim 21 , and (iii) a photoinitiator. 
     
     
       23. A coating composition according to  claim 22  wherein the colorant is present in a concentration of about 0.05 to 15 weight percent based on the weight of component (i) and the photoinitiator is present in a concentration of about 1 to 15 weight percent based on the weight of the polymerizable vinyl compound(s) present in the coating composition. 
     
     
       24. A polymeric coating composition comprising a polymer of one or more acrylic acid esters, one or more methacrylic acid esters and/or other copolymerizable vinyl compounds, having copolymerized therein one or more of the colorant compounds defined in  claim 21 . 
     
     
       25. A photopolymerizable colorant compound having the formula                    
       wherein 
       A is a residue of phthalocyanine or metal phthalocyanine;  
       R 1  is hydrogen, C 1 -C 6  alkyl, substituted C 1 -C 6  alkyl, C 3 -C 8  cycloalkyl, aryl or —R 2 -OQ;  
       R 2  is C 2 -C 8  alkylene, arylene, C 3 -C 8  cycloalkylene, arylene —C 1 -C 6  alkylene, arylene-oxy-C 1 -C 6  alkylene, arylenethio —C 1 -C 6  alyklene, 1,4-cyclohexylenedimethylene or —(—CH 2 CH 2 O) m —CH 2 CH 2 —;  
       m is 1-3;  
       n is 1-4;  
       Q is an ethylenically-unsaturated, photopolymerizable group selected from the following organic radicals;                    
       wherein 
       R 3  is hydrogen or C 1 -C 6  alkyl;  
       R 4  is hydrogen, C 1 -C 6  alkyl; phenyl; phenyl substituted with one or more groups selected from C 1 -C 6  alkyl, C 1 -C 6  alkoxy, —N(C 1 -C 6  alkyl) 2 , nitro, cyano, C 2 -C 6  alkoxycarbonyl, C 2 -C 6  alkanoyloxy or halogen; 1- or 2-naphthyl; 1- or 2-naphthyl substituted with C 1 -C 6  alkyl or C 1 -C 6  alkoxy; 2- or 3-thienyl; 2- or 3-thienyl substituted with C 1 -C 6  alkyl or halogen; 2- or 3- furyl; or 2- or 3-furyl substituted with C 1 -C 6  alkyl;  
       R 5  and R 6  are independently selected from hydrogen, C 1 -C 6  alkyl, substituted C 1 -C 6  alkyl, aryl or may be combined to represent a —(—CH 2 —)— 3-5  radical;  
       R 7  is hydrogen, C 1 -C 6  alkyl, substituted C 1 -C 6  alkyl, C 3 -C 8  alkenyl, C 3 -C 8  cycloalkyl or aryl; and  
       R 8  is hydrogen, C 1 -C 6  alkyl or aryl.  
     
     
       26. A coating composition comprising (i) one or more polymerizable vinyl compounds, (ii) one or more of the colorant compounds of  claim 25 , and (iii) a photoinitiator. 
     
     
       27. A coating composition according to  claim 26  wherein the colorant is present in a concentration of about 0.05 to 15 weight percent based on the weight of component (i) and the photoinitiator is present in a concentration of about 1 to 15 weight percent based on the weight of the polymerizable vinyl compound(s) present in the coating composition. 
     
     
       28. A polymeric coating composition comprising a polymer of one or more acrylic acid esters, one or more methacrylic acid esters and/or other copolymerizable vinyl compounds, having copolymerized therein one or more of the colorant compounds defined in  claim 25 .